O, o-dialkyl s-[(dicyano methyl) alkyl] phosphorothiolothionates



0,0-DIALKYL S-[tDICYANOMETHYLM PHOSPHOROTHIOLOTHIONATES V I Marvin A.McCall and Harry W. comer, 'lf -Kiiigsiw il,

Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey No Drawing. Filed Dec. 6, -1957, Ser. No.700,977

Claims. (.Cl. 260-3325) pesticides and in related uses. Consequently,it'is of considerable importance to discover new and usefulorganophosphorus compounds and to have a new process for the productionof organophosphorus compounds. Therefore, it is anobject of thisinvention to provide new and useful .organophosphorus compounds. It isanother .object of this invention to provide a novel method forpreparing the new and useful .organophosp'horus compounds. It is stillanother object of this invention to provide new and valuableinsecticides that can be used in various insecticidal compositions.

In accordance with this invention it hasbeen found that neworganophosphorus compounds, useful as insecticides, can be prepared byreacting phosphorothiolbthionates with certain 1,1-dicyanoethylenes. Thenew products of this invention have the structural formula:

where R, and R are selected from the group consisting of lower alkylradicals containing from 1 to 4' carbon atoms and alkoxy alkyl radicalswherein the alkoxy and alkyl groups containing from 1 to 4 carbon atoms,R is selected from the group consisting of hydrogen, lower alkylcontaining from 1- to 4 carbon atoms and phenyl, and R is selected fromthe group-consisting of hydrogen, alkoxy, containing 1 to 4 carbonatoms, alkylthio,;containing from 1 to 4 carbon atoms, halophenyl,nitrophenyl, thienyl, cycloalkyl, and pyridyl.

The compounds of this invention are formed by reacting aphosphorothiolothionate having the structural formula:

R\fi

/P--SH R10 wherein R and R are as defined above with a.1,'1-dicyanoethylene having the structural formula:

Rs\ /'CN R4 ON wherein R and R are as defined above.

In the practice of this invention we prefer to add one of the reactantsgraduallyto a' reactor containing the other reactant. For example, the1,1-dicyanoethylene ited States ate-n1: O

For example, they have been employed as inse'cticides, fungidides,

can be added gradually to .a reactor containing thephosphorothiolothionate.

Alternatively however, the reverse procedure of addition of reactantscan be used and the phosphorothiolothionate can be added to a reactorcontaining the 1,1-dicyanoethylene. Normally it is desirable to employ areactor provided-with adequate means of agitation and, since thereaction is quite exothermic, it is also desirable to employ a reactorthat is provided with adequate cooling means.

The operable temperature rangefor the reaction is generally from 25 to150 C. and the preferred temperature range is from 25 to C. However, itwill be realized that in some instances temperatures outside this rangecan be employed. The reaction time usually varies from 0.5 to 8 hours,but longer and shorter reaction periods are sometimes used. Normally itis unnecessary to employ a catalyst for the reaction since thephosphorothiolothionate will react with the 1,-1--d-icyanoethylene inthe absence of a catalyst. If it is considered desirable to employ acatalyst, there are certain catalysts that can be used. For example,nitrogen bases, such as pyridine and the tertiary amines, such astrialkyl amines, and the like, can be used.

Ordinarily, it is not necessary to employ a solvent for the reaction butin some instances solvents are desirable. Among the solvents that can beused are normally liquid aliphatic and aromatic hydrocarbons s'uclrl as"pentane, heptane, octane, benzene, toluene, the xylenes and 't'he like,chlorinated derivatives of the above-mentioned hydrocarbons as well asthe common ether and ester solvents. It is preferable to carry out thereaction using equimolar quantities of the reactants. However, the ratioof reactants is subject to wide variations.

16 plios'phorothiolothionates that are used in our inventi'on' can-beprepared by the known reaction-of 4 moles of an aliphatic alcohol withone mole of phosphorus pentasulfide. Many of :thel,'1 -dicyanoethylenesthat are used in our reaction can be prepared by reacting malonitrilewith the appropriate aldehyde according to Carson and Staughton,J.A.C.S. 5.0, 2825- (1928).

The following examples are illustrative of the compounds withinthe-scopeof this invention, their method of preparation-and theirutility as insecticides.

EXAMPLE 1 O,, O-diethyl S-(1-dicyanomethyl-l-methoxyethyl)phosphorothiolothion'ate:

cmo

GH:- *C\- i on s P.(s):(0 01m): Diethyl phosphorothiolothionate 0i1-mole) wasmix'ed with 1-methoxyethylidenemalonitrile (0.1 mole) and 5 or6 drops of triethyl amine ascatalyst. This mixture was then heated on asteam bath for 6 hours. A dark oily product was obtained which hadconsiderable anticholinesterase activity.

3 EXAMPLES 3, 4 AND 5 In like manner the following insecticidally activecompounds were prepared:

0,0-bis(2-methoxyethyl)S-( l-dicyanomethyl 1 ethoxyethyl)phosphorothiolothionate:

CHsC-C SP(S)(OC2H4OCH:)1

0,0-bis(2-chloroethyl)S-( l-dicyanomethyl 1 ethoxyethyl)phosphorothiolothionate:

OCIHE CHz-C-Cfi SP(S)(OC:H4C1), 0,0-diethylS-(1-dicyanomethyl-l-ethoxyethyl) phosphorothiolothionate:

- CaHsO CH:- -C

SP(S) (OCaHs): EXAMPLE 6 0,0-diethyl S-(2,2-dicyano-1-ethoxyethyl)phosphorothiolothionate:

This compound was prepared by the same procedure described above from0,0-diethyl phosphorothiolothionate and ethoxymethylenemalonitrile.

EXAMPLE 7 O-ethyl O-propyl S-(oc-dicyanomethyLa-ethoxybenzyl)phosphorothiolothionate:

OCzHs CN r i owf This compound was prepared by reaction of O-ethylO-propyl phosphorothiolothionate (0.1 mole) with ethoxybenzalmalonitrile(0.1 mole) in the presence of a few drops of pyridine as catalyst.

EXAMPLE 8 O-ethyl, O-methyl S-[2,2-dicyano-l-(ethylthio)ethyl]phosphorothiolothionate:

This compound was prepared from the reaction of O- y ethyl, O-methylphosphorothiolothionate (0.1 mole) and ethylthiomethylenemalonitrile(0.1 mole) in the presence of triethylamine as catalyst according to theprocedure given in Example 1.

EXAMPLE 9 0,0-diethyl S- [p chloro a (dicyanomethyl)benzyl]phosphorothiolothionate:

The compound was prepared by reacting p-chlorobenzalmalonitrile (0.1mole) in benzene solvent (25 ml.) with a few drops of tributylamine ascatalyst. The stirred reaction mixture was heater on the steam bath for8 hours then vacuum stripped at 1 mm. to remove the benzene solvent andany other volatile impurity that may be present.

EXAMPLE 1O 0,0-diethyl S[a-(dicyanomethyl)-m-nitrobenzy1]phosphorothiolothionate:

This compound was prepared by reacting meta-nitrobenzalmalonitrile (0.1mole) in benzene (25 cc.) with 0,0-diethyl phosphorothiolothionate (0.1mole) and 6 to 8 drops of triethylamine as catalyst. The reactionmixture was heated on the steam bath for 8 hours with stirring. Thebenzene was removed under 1 mm. pressure leaving a dark oily productwhich had pesticidal properties.

' EXAMPLE 11 0,0-diethyl SEO chloro a (dicyanomethyl)benzyl]phosphorothiolothionate:

SP (8) (O CHa-C C13):

This compound was prepared from the reaction of 0,0- bis (2,2,2trichloroethyl)phosphorothiolothionate (0.1

mole) and thienylidenemalonitrile (0.1 mole) in the presence oftripropylamine as the catalyst according to the procedure of Example 10.

EXAMPLE l3 0,0 -diethy1 S- l-dicyanomethyl) cyclohexylphosphorothiolothionate:

ON S CH This compound was prepared by the reaction of 0,0- diethylphosphorothiolothionate (0.1 mole) and cyclohexylidenemalonitrile (0.1mole) and triethylamine as catalyst according to the procedure ofExample 9.

EXAMPLE 14 0,0-diethy1 S-I-(Z-pyridyl) 2,2 dicyanoethylphosphorothiolothionate:

GEN -CHCE GEN This compound was prepared by adding 0,0-diethylphosphorothiolothionate (0.1 mole) and Z-pyridylmethylenemalonitrile(0.1 mole) in the presence of triethylamine catalyst according to theprocedure of Example 9.

EXAMPLE 15 This compound was prepared by adding vinylidene cyanide indry benzene as a diluent to 0,0-diethyl phosphorothiolothionate. Themixture was stirred for 30 to 40 minutes after the addition wascomplete, then heated on a steam bath for 3 hours. The benzene solventwas removed by vacuum stripping at 1 mm. pressure.

EXAMPLE 16 Use of compounds as insecticides Tests against mites werecarried out in the following manner. Acetone solutions containing 1% ofthe candidate compounds were prepared and diluted with water to givesolutions of the desired concentration for testing. Two heavily infestedbean leaves containing adult twospotted mites (Tetranychus bimaculatusHarvey) were carefully dipped in the above solutions and dried in agentle air stream. The leaves were then placed on damp paper toweling inPetri dishes and observed after 24 hours for mortality among the adultmites.

It should be noted that tests using acetone-water solutions (containingnone of the toxicant) kill none of the mites.

The compounds of Examples 2-7, 9, 13, 14 and 15 were similarly effectivewhen used in the above tests.

The pmticidal data for several monocyanoalkyl derivatives are givenbelow in Table II. By comparison it can be seen that the dicyanoalkylderivatives of our invention are several times more active than thesimple monocyanoalkyl derivatives disclosed in the prior art andtherefore the compounds of this invention are not only differentstructurally but also unexpectedly several times more active.

TABLE II Ooncentra- Percent Simple Cyanoalkyl Phosphorothiolothionatestion in Kill t p.p.m. Mites 1. 0,0-Diethyl S-(2-cyano-l-methylethyl)phosphorothiolothionate. 100 77 i i8 (C2Hs02)P-SC 1HCH2CN 2. 0,0-Diethy1S-(cyanomethyDphosphorothiolothionate. 100 85 3O 60 H 10 15(CzH5O)zPS-CH7CN 6 We claim: 1. As a composition of matter, 0,0-diethylS-(l-dicyanomethyl-l-ethoxyethyl) phosphorothiolothionate:

CIHEO CN CH: *OH

SP (5) (O CzHs):

2. As a composition of matter, O-ethyl, O-methyl S- [2,2-dicyano 1-(ethylthio) ethyl] phosphorothiolothionate:

3. As a composition of matter, 0,0-diethylSEO-chlorowdicyanomethyD-benzyl] phosphorothiolothionate:

(51 I ON 4. As a composition of matter, 0,0-bis(2,2,2-trichloroethyl)S-[2,2-dicyano-1-(2-thienyl)ethyl] phosphorothiolothionate:

ON CH-Cfi s I SP (S) (O CH -C C13):

5. The organophosphorus compounds having the structural formula:

References Cited in the file of this patent Chemical Abstracts: vol. 48,p. 5561'; p. 557a (1954). (Abstract of N. N. Melnikov et a1., DokladyAkad. Nauk, U.S.S.R., vol. 86, pp. 543-6 (1952).)

Chemical Abstracts, vol. 48, p. 6639d (1954). (Abstract of K. A. Gar etal., Doklady Akad. Nauk, U.S.S.R., vol. 94, pp. 241-4, 1954.)

UNITED STATES PATENT OFFICE CE'HFICATION OF CORRECTION PatemNo-2,957,007 October 18, 1360*" Marvin A McCall et a1 a It is herebycertified that error appears in the above numbered pat ent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 2 lines 47 to 51 the formula should appear as shown below insteadof as in the patent:

CH3O /CN g'C CH SP(S) (OC H column l, line 4, for "heater" read heatedcolumn 5, Table 11, first column thereof, after item one, the formulashould appear as shown below instead of as in the patent:

S CH

(c H o) PS;-CH-CH CN 2 5 2 2 Signed and sealed this 18th day of April19610 7 (SEAL) Attest:

ERNEST SWIDER I DAVID L. LADD Attesting Officer Commissioner of Patents

1. AS A COMPOSITION OF MATTER, O,O-DIETHYLS-(1-DICYANOMETHYL-1-ETHOXYETHYL) PHOSPHOROTHIOLOTHIONATE:
 5. THEORGANOPHOSPHORUS COMPOUNDS HAVING THE STRUCTURAL FORMULA: